Thiazolo [4,5-b] pyridines as fungicides

ABSTRACT

A method for controlling harmful fungi, which comprises treating the fungi or the materials, plants, the soil or the seed to be protected against fungal attack and/or animal pests with an effective amount of at least one thiazolo[4,5-b]pyridine of the formula I:  
                 
 
     in which n is 0, 1 or 2, the substituents R 1 , R 2 , R 3 , have the following meanings:  
     R 1 , R 2 , R 3 : independently of one another are: hydrogen, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl or phenyl which may be unsubstituted or carry 1, 2, 3 or 4 substituents which are selected, independently of one another, from halogen, nitro, cyano, alkyl, alkoxy, OCHF 2  or CF 3 ; and wherein  
     A and R are as defined in claim 1

[0001] The present invention relates to novel thiazolo[4,5-b]pyridines and a method for controlling harmful fungi.

[0002] Thiazole compounds, wherein the thiazole ring is fused to a 6 membered aromatic ring have several times been described in the literature as pharmaceutically active compounds. For example, EP-A 405967 discloses fused azolopyridines which carry an organic thio radical or an organic sulfinyl radical on the five membered heterocycle. WO 93/24480 discloses several azolobenzenes and azolopyridines, which carry a 2-pyridylmethylthio radical or a 2-pyridylmethylsulfinyl radical, to have an antibacterial effect against Heliobacter pylori. Similar compounds are known from JP 62-207271 to be useful as antiulcer agents.

[0003] WO 97/28128 discloses 6-bromo-2-methylthio-thiazolo[4,5-b]pyridine and 6-bromo-2-methylsulfonyl-thiazolo[4,5-b]pyridine as intermediates in the preparation of novel inhibitors for the enzyme oxido squalene cyclase.

[0004] EP-A 1000946 describes the pesticidal and parasitical use of several 2-(substituted thio)thiazolo[4,5-b]pyridines.

[0005] So far, no thiazolo[4,5-b]pyridines have been described, which are useful as fungicides.

[0006] In principle, there is a constant need for novel fungicides to be provided, in order to broaden the activity spectrum and to circumvent a possible formation of resistance against the known fungicides.

[0007] It is an object of the present invention to provide a new method for combatting harmful fungi and also new compounds which are useful for controlling harmful fungi.

[0008] We have found that this object is surprisingly achieved by thiazolo[4,5-b]pyridines of the formula I defined below.

[0009] Therefore, the present invention relates to a method for controlling harmful fungi, which comprises treating the fungi or the materials, plants, the soil or the seed to be protected against fungal attack and/or animal pests with an effective amount of at least one thiazolo[4,5-b]pyridine of the formula I:

[0010] in which the substituents R₁, R², R³, A and the index n have the following meanings:

[0011] R₁, R², R³: independently of one another are: hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-alko-XY -C₁-C₄-alkyl or phenyl which may be unsubstituted or carry 1, 2, 3 or 4 substituents which are selected, independently of one another, from halogen, nitro, cyano, alkyl, alkoxy, OCHF₂ or CF₃;

[0012] n: 0, 1 or 2;

[0013] R: hydrogen, cyano, halogen, C₁-C₆-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl, C₂-C₄-alkinyl, C₂-C₄-haloalkinyl, cyano-C₁-C₄-alkyl, C₁-C₄-alko-XY -C₁-C₄-alkyl, C₃-C₈-cycloalkyl, tris(C₁-C₄-alkyl)silyl, tris(C₁-C₄-alkyl)silyloxy, COR⁴, COOR⁵, CONR⁶R⁷, S(O)_(k)R⁸, phenyl, phenoxy, a 5 or 6 membered heterocycle, which has 1, 2, or 3 heteroatoms being selected from O, S and N, and which may be saturated, unsaturated or aromatic, wherein phenyl, phenoxy and the heterocycle, independently of each other, may carry 1, 2, 3 or 4 substituents which are selected, independently of one another, from halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, methylsulfonyl, OCHF₂, CF,₃ or phenyl, which may carry 1, 2 or 3 radicals selected from halogen, C₁-C₄-alkyl, methylsulfonyl, OCHF₂ or CF₃; wherein

[0014] k is 0, 1 or 2;

[0015] R⁴ is hydrogen, C₁-C₆-alkyl, phenyl and phenyl-C₁-C₄-alkyl, wherein phenyl and phenyl-C₁-C₄-alkyl may carry 1, 2, 3 or 4 substituents on the phenyl ring which are selected, independently of one another, from halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, OCHF₂ or CF₃;

[0016] R⁵ is C₁-C₆-alkyl, C₁C₄-alkoxy-C₁-C₄alkyl, phenyl and phenyl-C₁-C₄-alkyl, wherein phenyl and phenyl-C₁-C₄-alkyl may carry 1, 2, 3 or 4 substituents on the phenyl ring which are selected, independently of one another, from halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, OCHF₂ or CF₃;

[0017] R⁶, R⁷ independently from one another are hydrogen, C₁-C₆-alkyl, C₁-C4-alkoxy-C₁-C₄-alkyl, phenyl, and phenyl-C₁-C₄-alkyl, wherein phenyl and phenyl-C₁-C₄-alkyl may carry 1, 2, 3 or 4 substituents on the phenyl ring, which are selected, independently of one another, from halogen, nitro, cyano, C₁-C4-alkyl, C₁-C₄-alkoxy, OCHF₂ or CF₃; or may together form a 5-or 6-membered heterocycle, which may additionally to the nitrogen atom may have 1 or 2 further heteroatoms selected from N, O or S,

[0018] R⁸ is C₁-C₆-alkyl, C₁-C₄-haloalkyl, phenyl, and phenyl-C₁-C₄-alkyl, wherein phenyl and phenyl-C₁-C₄-alkyl may carry 1, 2, 3 or 4 substituents on the phenyl ring which are selected, independently of one another, from halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, OCHF₂ or CF₃;

[0019] A: C₁-C₄-alkylene; or

[0020] A-R: may together be dihalomethyl, trihalomethyl, C₃-C₈-cycloalkyl, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl, C₅-C₈-cycloalkenyl or a 5 or 6 membered heterocycle, which has 1, 2, or 3 heteroatoms being selected from O, S and N, which may be saturated, unsaturated or aromatic, and which may carry 1, 2, 3 or 4 substituents which are selected, independently of one another, from halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, methylsulfonyl, OCHF₂, CF₃ or phenyl, which may carry 1, 2 or 3 radicals selected from halogen, C₁-C₄-alkyl, methylsulfonyl, OCHF₂ or CF₃, wherein cycloalkyl and cycloalkenyl, may independently carry 1, 2, 3 or 4 substituents, which are selected, independently of one another, from halogen and C₁-C₄-alkyl, and/or may contain a carbonyl or thiocarbonyl ring member;

[0021] and/or at least one agriculturally acceptable salts thereof.

[0022] The invention also relates to thiazolo[4,5-b]pyridine compounds of the formula I as defined above, except:

[0023] 2-methylsulfonyl-thiazolo[4,5-b]pyridine,

[0024] 2-methylsulfonyl-6-bromo-thiazolo[4,5-b]pyridine,

[0025] 2-methylthio-6-bromo-thiazolo[4,5-b ]pyridine,

[0026] 2-[(methoxycarbonyl)methylsulfinyl]thiazolo[4,5-b]pyridine,

[0027] 2-[(methoxycarbonyl)methylsulfinyl]-6-trifluoro-thiazolo[4,5-b]pyridine,

[0028] 2-[(methoxycarbonyl)methylthio]-6-trifluoro-thiazolo[4,5-b]pyridine, and

[0029] 2-[(methoxycarbonyl)methylthio]thiazolo[4,5-b]pyridine,

[0030] 2-[(ethoxycarbonyl)methylthio]thiazolo[4,5-b]pyridine,

[0031] 2-[(4,4,3-trifluoro-3-butenyl)thio]hiazolo[4,5-b]pyridine

[0032] 2-[(2-propen-1-yl)thio]thiazolo[4,5-b]pyridine,

[0033] 2-[(cycloproplymethyl)thio]thiazolo[4,5-b]pyridine,

[0034] 2-[1-(ethoxycarbonyl)ethylthio]thiazolo[4,5-b]pyridine,

[0035] 2-[(bromodifluoromethyl)thio]thiazolo[4,5-b]pyridine,

[0036] 2-[(difluoromethyl)thio]thiazolo[4,5-b]pyridine, and

[0037] 2-[(2,2,2-trifluoroethyl)thio]hiazolo[4,5-b]pyridine.

[0038] The invention furthermore relates to agricultural formulations, preferably in the form of a powder, suspension, dispersion, emulsion, emulsion concentrate, oil dispersion, paste, dust, a directly sprayable solution, a material for spreading, or in the form of granules, which comprises at least one thiazolo[4,5-b]pyridine compound of the formula I and/or at least one agriculturally acceptable salt thereof and at least one agriculturally acceptable carrier, which may be liquid or solid.

[0039] In the substituents, the thiazolo[4,5-b]pyridines of the formula I may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. The present invention provides both the pure enantiomers or diastereomers and mixtures thereof.

[0040] Suitable agriculturally useful salts are especially the salts of those counterions which do not have any adverse effect on the herbicidal action of the thiazolo[4,5-b]pyridines I. Preferred agriculturally usefull salts are selected from the acid addition salts of the thiazolo[4,5-b]pyridines I.

[0041] Preferred anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and also the anions of C₁-C₄-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting thiazolo[4,5-b]pyridines I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

[0042] The organic moieties mentioned in the definitions of the radicals A, R, R¹ to R⁸ or as radicals on cycloalk(en)yl, phenyl or heterocyclic rings are—like the term halogen—collective terms for individual listings of the individual group members. All carbon chains, i.e. all alkyl, haloalkyl, alkoxy, haloalkoxy, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkenyl, haloalkenyl, alkynyl and haloalkynyl groups, and the corresponding moieties in larger groups, such as alkoxycarbonyl, alkoxycarbonylalkyl, etc., can be straight-chain or branched, where the prefix C_(n)C_(m) indicates in each case the possible number of carbon atoms in the group. Halogenated substituents preferably carry one, two, three, four or five identical or different halogen atoms. The term halogen represents in each case fluorine, chlorine, bromine or iodine. Further examples of meanings are:

[0043] C₁-C₄-alkyl and the alkyl moieties of C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylamino, di-C₁-C₄-alkylamine or C₁-C₄-alkylcarbonyloxy: saturated, straight-chain or branched hydrocarbon radicals having 1 to 4 carbon atoms, specifically methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl;

[0044] C₁-C₆-alkyl: saturated, straight-chain or branched hydrocarbon radicals having 1 to 6 carbon atoms, for example C₁-C₄-alkyl as mentioned above or pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;

[0045] C₁-C₄-alkylene: methylene, 1,1-ethylene, 1,2-ethylene, 1,1-propylene, 1,2-propylene, 2,2-propylene, 1,3-propylene, 2-methyl-1,2-propylene, 2-methyl-1,3-propylene, 1,1-butylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 2,2-butylene, or 2,3-butylene;

[0046] dihalomethyl: methyl which carrys 2 halogenatoms, e.g. dichloromethyl, difluoromethyl, chlorofluoromethyl,

[0047] trihalomethyl: methyl which carrys 3 halogenatoms, e.g. trichloromethyl, trifluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, bromodifluoromethyl;

[0048] C₁-C₄-haloalkyl and the haloalkyl moieties of C₁-C₄-haloalkoxy: straight-chain or branched alkyl groups having 1 to 4 carbon atoms (as mentioned above), where the hydrogen atoms in these groups may be partially or fully replaced by halogen atoms as mentioned above, especially C₁-C₂-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,22-trichloroethyl and pentafluoroethyl;

[0049] C₁-C₄-alkoxy: OCH₃, OC₂H₅, n-propoxy, OCH(CH₃)₂, n-butoxy, OCH(CH₃)—C₂H₅, OCH₂—CH(CH₃)₂ or OC(CH₃)₃, preferably OCH₃, OC₂H₅, or OCH(CH₃)₂;

[0050] C₁-C₄-haloalkoxy: a C₁-C₄-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e. for example OCH₂F, OCHF₂, OCF₃, OCH₂Cl, OCH(Cl)₂, OC(Cl)₃, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC₂F₅, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, OCF₂—C₂F₅, 1-(CH₂F)-2-fluoroethoxy, 1-(CH₂Cl)-2-chloroethoxy, 1-(CH₂Br)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy, preferably OCHF₂, OCF₃, dichlorofluoramethoxy, chlorodifluoromethoxy or 2,2,2-trifluoroethoxy;

[0051] C₁-C₄-alkoxy-C₁-C₄-alkyl: C₁-C₄-alkyl which is substituted by C₁-C₄-alkoxy as mentioned above, i.e. for example CH₂—OCH₃, CH₂—OC₂H₅, n-propoxymethyl, CH₂—OCH(CH₃)₂, n-butoxymethyl, (1-methylpropoxy)methyl, (2-methylpropoxy)methyl, CH₂—OC(CH₃)₃, 2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n-propoxy)ethyl, 2-(1-methylethoxy)ethyl, 2-(n-butoxy)ethyl, 2-(1-methylpropoxy)ethyl, 2-(2-methyl-propoxy)ethyl, 2-(1,1-dimethylethoxy)ethyl, 2-(methoxy)-propyl, 2-(ethoxy)propyl, 2-(n-propoxy)propyl, 2-(1-methylethoxy)propyl, 2-(n-butoxy)propyl, 2-(1-methylpropoxy)propyl, 2-(2-methylpropoxy)propyl, 2-(1,1-dimethylethoxy)propyl, 3-(methoxy)propyl, 3-(ethoxy)propyl, 3-(n-propoxy)propyl, 3-(1-methylethoxy)propyl, 3-(n-butoxy)propyl, 3-(1-methyl-propoxy)propyl, 3-(2-methylpropoxy)propyl, 3-(1,1-dimethyl-ethoxy)propyl, 2-(methoxy)butyl, 2-(ethoxy)butyl, 2-(n-propoxy)butyl, 2-(1-methylethoxy)butyl, 2-(n-butoxy)-butyl, 2-(1-methylpropoxy)butyl, 2-(2-methylpropoxy)butyl, 2-(1,1-dimethylethoxy)butyl, 3-(methoxy)butyl, 3-(ethoxy)-butyl, 3-(n-propoxy)butyl, 3-(1-methylethoxy)butyl, 3-(n-butoxy)butyl, 3-(1-methylpropoxy)butyl, 3-(2-methyl-propoxy)butyl, 3-(1,1-dimethylethoxy)butyl, 4-(methoxy)butyl, 4-(ethoxy)butyl, 4-(n-propoxy)butyl, 4-(1-methylethoxy)butyl, 4-(n-butoxy)butyl, 4-(1-methylpropoxy)butyl, 4-(2-methyl-propoxy)butyl or 4-(1,1-dimethylethoxy)butyl, preferably CH₂—OCH₃, CH₂—OC₂H₅, 2-methoxyethyl or 2-ethoxyethyl;

[0052] C₃-C₄-alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 3 to 4 carbon atoms and a double bond in any position, preferably in the 1 position, for example 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl and 2-methyl-2-propenyl;

[0053] C₂-C₄-alkenyl and the alkenyl moieties of C₂-C₄-alkenyloxy: ethenyl or C₃-C₄-alkenyl (as mentioned above);

[0054] C₂-C₄-haloalkenyl and the haloalkenyl moieties of C₂-C₄-haloalkenyloxy: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4 carbon atoms and a double bond in any position (as mentioned above), where the hydrogen atoms in these groups may be partially or fully replaced by halogen atoms as mentioned above, in particular by fluorine, chlorine and bromine;

[0055] C₃-C₄-alkynyl: straight-chain or branched hydrocarbon radicals having 3 to 4 carbon atoms and a triple bond in any position, preferably in the 1 position, for example ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl and 1-methyl -2-propynyl;

[0056] C₂-C₄-alkynyl and the alkynyl moieties of C₂-C₄-alkynyloxy: ethynyl or C₃-C₄-alkynyl (as mentioned above);

[0057] C₂-C₄-haloalkynyl and the haloalkynyl moieties of C₂-C₄-halo-alkynyloxy: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4 carbon atoms and a triple bond in any position (as mentioned above), where the hydrogen atoms in these groups may be partially or fully replaced by halogen atoms as mentioned above, in particular by fluorine, chlorine and bromine;

[0058] C₃-C₈-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl;

[0059] C₃-C₈-cycloalkyl containing a carbonyl or thiocarbonyl ring member: for example cyclobutanon-2-yl, cyclobutanon-3-yl, cyclopentanon-2-yl, cyclopentanon-3-yl, cyclohexanon-2-yl, cyclohexanon-4-yl, cycloheptanon-2-yl, cyclooctanon-2-yl, cyclobutanethion-2-yl, cyclobutanethion-3-yl, cyclopentanethion -2-yl, cyclopentanethion-3-yl, cyclohexanethion-2-yl, cyclohexanethion-4-yl, cycloheptanethion-2-yl or cyclooctanethion-2-yl, preferably cyclopentanon-2-yl or cyclohexanon-2-yl;

[0060] C₅-C₈-cycloalkenyl: cyclopenten-2-yl, cyclohexen-2-yl, cyclohepten-2-yl, cycloocten-2-yl, cyclopenten-1-yl, cyclohexen-3-yl, cyclohepten-3-yl, cyclooten-3-yl or cycloocten-4-yl;

[0061] cyano-C₁-C₄-alkyl: cyanomethyl, 1-cyanoethyl, 2-cyanoethyl, 1-cyanoprop-1-yl, 2-cyanoprop-1-yl, 3-cyanoprop-1-yl, 1-cyanobut-1-yl, 2-cyanobut-1-yl, 3-cyanobut -1-yl, 4-cyanobut-1-yl, 1-cyanobut-2-yl, 2-cyanobut-2-yl, 3-cyanobut-2-yl, 4-cyanobut-2-yl, 1-cyanomethyleth-1-yl, 1-cyanomethyl-1-methyleth-1-yl or 1-cyanomethylprop-1-yl, preferably cyanomethyl or 2-cyanoethyl;

[0062] tris(C₁-C₄-alkyl)silyl and the tris(C₁-C₄-alkyl)silylresidue in tris(C₁-C₄-alkyl)silyloxy: a radical of the formula R^(a) ₃Si, where R^(a) is C₁-C₄-alkyl and may be the same or different, e.g. trimethylsilyl, triethylsilyl, dimethylethylsilyl, dimethyl-isopropylsilyl, dimethyl-n-butylsilyl or dimethyl-tert-butylsilyl;

[0063] The 5 or 6-membered heterocycles which have 1, 2, or 3 heteroatoms being selected from O, S and N can be saturated, partially or fully unsaturated or aromatic. Saturated 5- or 6-membered heterocycles may also contain a carbonyl or thiocarbonyl ring member.

[0064] Examples of saturated heterocycles containing a carbonyl or thiocarbonyl ring member are; tetrahydrofuran-2-yl, tetrahydrofuran -3-yl, tetrahydrothiophen-2-yl, tetrahydrothiophen -3-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, 1,3-dioxolan-2-yl, 1,3-dioxolan-4-yl, 1,3-oxathiolan-2-yl, 1,3-oxathiolan-4-yl, 1,3-oxathiolan-5-yl, 1,3-oxazolidin -2-yl, 1,3-oxazolidin-3-yl, 1,3-oxazolidin-4-yl, 1,3-oxazolidin -5-yl, 1,2-oxazolidin-2-yl, 1,2-oxazolidin-3-yl, 1,2-oxazolidin-4-yl, 1,2-oxazolidin-5-yl, 1,3-dithiolan-2-yl, 1,3-dithiolan-4-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin -5-yl, tetrahydropyrazol-1-yl, tetrahydropyrazol-3-yl, tetrahydropyrazol-4-yl, tetrahydropyran-2-yl, tetrahydropyran -3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran -3-yl, tetrahydropyran-4-yl, piperidin-1-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, 1,3-dioxan -2-yl, 1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl, 1,3-oxathian-2-yl, 1,3-oxathian-4-yl, 1,3-oxathian-5-yl, 1,3-oxathian-6-yl, 1,4-oxathian-2-yl, 1,4-oxathian-3-yl, morpholin -2-yl, morpholin-3-yl, morpholin-4-yl, hexahydropyridazin -1-yl, hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, hexahydropyrimidin-1-yl, hexahydropyrimidin-2-yl, hexahydropyrimidin -4-yl, hexahydropyrimidin-5-yl, piperazin-1-yl, piperazin -2-yl, piperazin-3-yl, hexahydro-1,3,5-triazin-1-yl, hexahydro-1,3,5-triazin-2-yl.

[0065] Examples of partially unsaturated heterocycles are: dihydrofuran-2-yl, 1,2-oxazolin-3-yl, 1,2-oxazolin-5-yl, 1,3-oxazolin-2-yl.

[0066] Examples of aromatic heterocycles are furyl, such as 2-furyl and 3-furyl, thienyl, such as 2-thienyl and 3-thienyl, pyrrolyl, such as 2-pyrrolyl and 3-pyrrolyl, isoxazolyl, such as 3-isoxazolyl, 4-isoxazolyl and 5-isoxazolyl, isothiazolyl, such as 3-isothiazolyl, 4-isothiazolyl and 5-isothiazolyl, pyrazolyl, such as 3-pyrazolyl, 4-pyrazolyl and 5-pyrazolyl, oxazolyl, such as 2-oxazolyl, 4-oxazolyl and 5-oxazolyl, thiazolyl, such as 2-thiazolyl, 4-thiazolyl and 5-thiazolyl, imidazolyl, such as 2-imidazolyl and 4-imidazolyl, oxadiazolyl, such as 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl and 1,3,4-oxadiazol-2-yl, thiadiazolyl, such as 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl and 1,3,4-thiadiazol-2-yl, triazolyl, such as 1,2,4-triazol-1-yl, 1,2,4-triazol-3-yl and 1,2,4-triazol-4-yl, pyridinyl, such as 2-pyridinyl, 3-pyridinyl and 4-pyridinyl, pyridazinyl, such as 3-pyridazinyl and 4-pyridazinyl, pyrimidinyl, such as 2-pyrimidinyl, 4-pyrinidinyl and 5-pyrimidinyl, and furthermore 2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl, in particular pyridyl, pyrimidyl, furanyl and thienyl.

[0067] With respect to their intended use as fungicides, preference is given to thiazolo[4,5-b]pyridines of the formula I, wherein at least one of the radicals R¹ to R³ and particularly preferred R² is different from hydrogen. Particular preference is given to those thiazolo[4,5-b]pyridines of the formula I wherein the radicals R¹ to R³ are as defined below, in each case on their own or in combination:

[0068] R¹ hydrogen or C₁-C₄-alkyl, especially hydrogen, or methyl;

[0069] R² hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, especially hydrogen, chlorine, bromine, methyl or trifluoromethyl;

[0070] R³ hydrogen;

[0071] In a preferred embodiement of the invention the variable A in formula I is selected from methylene, 1,2-ethylene, 1,1-ethylene or 1,3-propylene.

[0072] In a particularly preferred embodiement of the invention R in formula I is phenyl, phenoxy, a 5 or a 6 membered heterocycle, which has 1, 2, or 3, preferably 1 or 2 heteroatoms being selected from O, S and N, and which may be saturated, unsaturated or aromatic. Phenyl, phenoxy and the heterocycle, independently of each other, may be unsubstituted or substituted as defined above. Preferred substituents on phenyl, phenoxy and heterocyclyl are: F, Cl, methyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, or phenyl which is unsubstituted or substituted as defined above. In this embodiement, preference is given to thiazolo[4,5-b]pyridines I, where R is phenyl, phenoxy, furyl, thiophenyl, or pyridyl, each of which may be unsubstituted or substituted as defined above.

[0073] In another preferred embodiement of the invention R is selected from cyano, C₁-C₄-alkoxy, cyano-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, tris(C₁-C₄-alkyl)silyl, tris(C₁-C₄-alkyl)silyloxy, COR⁴, COOR⁵, CONR⁶R⁷ or S(O)_(k)R⁸, wherein the radicals R⁴ to R⁸ and the integer k are defined as above. The integer k is preferably 2. Preferably R4 to R⁸ have the meanings listed below:

[0074] R⁴ is C₁-C₄-alkyl and phenyl which may carry 1, 2, 3 or 4 substituents on the phenyl ring being selected, independently of one another, from halogen and C₁-C₄-alkyl;

[0075] R⁵ is C₁-C₆-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, phenyl, and phenyl -C₁-C₄-alkyl, wherein phenyl and phenyl-C₁-C₄-alkyl may carry 1 or 2 substituents on the phenyl ring which are selected, independently of one another, from halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, OCHF₂ and CF₃;

[0076] R⁶,R⁷ independently from one another are hydrogen, C₁-C₆-alkyl, or may together with the nitrogen atom form a morpholinyl, piperidinyl, piperazinyl or pyrrolidinyl radical;

[0077] R⁸ is phenyl, which may carry 1 or 2 substituents being selected, independently of one another, from halogen, C₁-C₄-alkyl and CF₃.

[0078] Preference is given to thiazolo[4,5-b]pyridines of the formula I, where the variable n is 1 or 2.

[0079] Representative examples of thiazolo[4,5-b]pyridines of the formula I, wherein R³ is hydrogen are listed in table 1. TABLE 1 thiazolo[4,5-b]pyridines I.1 to I.311. HPLC MS¹⁾ MM²) Ex. R¹ R² n A-R [t in s] [m/z] [D] 1. H Cl 0 n-C₄H₉ 2. H Cl 0 (CH₂)₂CH═CH₂ 3. H Cl 0 (CH₂)₂Ph 4. H Cl 0 (CH₂)₂(4-ClPh) 5. H Cl 0 i-C₃H₇ 6. H Cl 0 CH₂OCH₃ 7. H Cl 0 n-C₃H₇ 8. H Cl 0 CH₂(c-C₃H₅) 9. H Cl 0 c-C₄H₈ 10. H Cl 0 c-C₅H₁₀ 11. H Cl 0 C₂H₅ 12. H Cl 0 CH₂CH═CH₂ 13. H Cl 0 (CH₂)₃COOC₂H₅ 14. H Cl 0 CH₂(4-ClPh) 15. H Cl 0 CH₂CH₂OPh 16. H Cl 0 CH₂(4-(CF₃)Ph) 17. H Cl 0 CH₂Ph 18. H Cl 0 CH₂COOCH₃ 19. H Cl 0 CH₂CONH₂ 20. H Cl 0 n-C₇H₁₅ 21. H Cl 0 (CH₂)₅CN 22. H Cl 0 (CH₂)₃Cl 23. H Br 0 C₂H₅ 24. H Br 0 n-C₄H₉ 25. H Br 0 CH₂-i-C₃H₇ 26. H Br 0 CH₂CH₂-t-C₄H₉ 27. H Br 0 CH₂CH₂-i-C₃H₇ 28. H Br 0 i-C₃H₇ 29. H Br 0 CH₂-c-C₃H₅ 30. H Br 0 CH₂-c-C₄H₇ 31. H Br 0 CH₂-c-C₆H₁₁ 32. H Br 0 CH₂[4-(CF₃)Ph] 33. H Br 0 CH₂Ph 34. H Br 0 c-C₅H₉ 35. H Br 0 c-C₆H₁₁ 36. H Br 0 c-C₇H₁₃ 37. H Br 0 c-C₈H₁₅ 38. H Br 0 2-cyclohexenyl 39. H Br 0 CH₂CH═CH₂ 40. H Br 0 CH₂C(CH₃)═CH₂ 41. H Br 0 CH₂C≡CH 42. H Br 0 CH₂Si(CH₃)₃ 43. H Br 0 CH₂O-n-C₈H₁₇ 44. H Br 0 CH₂SCH₃ 45. H Br 0 CH₂O(4-ClPh) 46. H Br 0 CH₂SO₂Ph 47. H Br 0 CH₂CH₂CN 48. H Br 0 (CH₂)₃COOC₂H₅ 49. H Br 0 CH₂COPh 50. H Br 0 CH₂CONH₂ 51. H Br 0 CH₂CH₂OPh 52. H Br 0 (CH₂)₃-(4-Pyridyl) 53. H CH₃ 0 n-C₄H₉ 54. H CH₃ 0 CH₂CH₂-t-C₄H₉ 55. H CH₃ 0 CH₂CH₂-i-C₃H₇ 56. H CH₃ 0 i-C₃H₇ 57. H CH₃ 0 CH₂Si(CH₃)₂(t-C₄H₉) 58. H CH₃ 0 CH₂-c-C₃H₅ 59. H CH₃ 0 c-C₆H₁₂ 60. H CH₃ 0 c-C₅H₉ 61. H CH₃ 0 CH₂Ph 62. H CH₃ 0 CH(CH₃)Ph 63. H CH₃ 0 (CH₂)₃-(4-Pyridyl) 64. H CH₃ 0 CH₂CH₂OPh 65. H CH₃ 0 CH₂O(4-ClPh) 66. H CH₃ 0 CH₂COCH₃ 67. H CH₃ 0 CH₂CO-t-C₄H₉ 68. H CH₃ 0 CH(CH₃)CONH₂ 69. H CH₃ 0 CH₂SO₂Ph 70. H H 0 CH₂Ph 3.115 259 258.37 71. H H 0 CH₂-i-C₃H₇ 3.133 225.05 224.35 72. H H 0 CH₂CH₂OPh 3.139 289.05 288.39 73. H H 0 2-(CH₃O—CH₂CH₂O)C₂H₄ 2.169 271.05 270.37 74. H H 0 CH═CH₂ 2.785 209 208.31 75. H H 0 n-C₄H₉ 3.182 225.05 224.35 76. H H 0 CH₂[3-(CF₃)Ph] 3.224 327 326.36 77. H H 0 CH₂CF₃ 2.788 251.95 250.27 78. H H 0 CH₂(3-ClPh) 3.288 293.95 292.81 79. H H 0 CH₂CH₂[4-(NO₂)Ph] 2.929 318 317.39 80. H H 0 CH₂[3-(OCF₃)Ph] 3.287 344 342.36 81. H H 0 CH₂[4-(OCF₃)Ph] 3.322 303.05 302.42 82. H H 0 CH₂C(CH₃)═CH₂ 2.983 223 222.33 83. H H 0 CH₂[3,5-(OCH₃)₂Ph] 2.914 319.05 318.42 84. CH₃ Br 0 CH₂Ph 3.435 352 351.29 85. CH₃ Br 0 CH₂-i-C₃H₇ 3.503 318.05 317.27 86. CH₃ Br 0 2-(C₂H₅O)Ph 3.510 382.05 381.32 87. CH₃ Br 0 2-(CH₃O—CH₂CH₂O)C₂H₄ 2.708 364.05 363.3 88. CH₃ Br 0 CH═CH₂ 3.175 302.95 301.23 89. CH₃ Br 0 n-C₄H₉ 3.528 318 317.27 90. CH₃ Br 0 CH₂[3-(CF₃)Ph] 3.546 420.05 419.29 91. CH₃ Br 0 CH₂CF₃ 3.106 344.95 343.19 92. CH₃ Br 0 CH₂(3-ClPh) 3.583 386.95 385.73 93. CH₃ Br 0 CH₂CH₂[4-(NO₂)Ph] 3.289 410.95 410.31 94. CH₃ Br 0 CH₂[3-(OCF₃)Ph] 3.597 436.95 435.29 95. CH₃ Br 0 CH₂[4-(OCF₃)Ph] 3.646 396.05 395.34 96. CH₃ Br 0 CH₂C(CH₃)═CH₂ 3.338 316.95 315.26 97. CH₃ Br 0 CH₂[3,5-(OCH₃)₂Ph] 3.267 412.05 411.34 98. CH₃ Br 0 c-C₅H₉ 3.55 330.05 329.28 99. CH₃ Br 0 2-thiophenyl 3.086 344.05 343.29 100. CH₃ Br 0 CH═C(CH₃)₂ 3.186 316.05 315.26 101. CH₃ Br 0 CH₂-tetrahydropy- 3.495 376.05 375.37 ran-3-yl 102. CH₃ Br 0 CH₂CH₂CH═CH₂ 3.394 316.05 315.26 103. CH₃ Br 0 n-C₃H₇ 3.359 304.05 303.24 104. CH₃ Br 0 CH₂-t-C₄H₉ 3.661 332.05 331.3 105. CH₃ Br 0 C(CH₃)═CH₂ 3.208 302.95 301.23 106. CH₃ Br 0 c-C₄H₇ 3.376 316.05 315.26 107. CH₃ Br 0 CH₂[2,6-(F)₂Ph] 3.420 388.95 387.27 108. CH₃ Br 0 3-thiophenyl 3.038 344.5 343.29 109. CH₃ Br 0 CH₂CHF₂ 3.113 326.8 325.2 110. CH₃ Br 0 CH₂-c-C₃H₅ 3.383 316.05 315.26 111. CH₃ Br 0 CH₂[2-(Ph)Ph] 3.812 428.05 427.39 112. CH₃ Br 0 CH₂[3,4-(Cl)₂Ph] 3.870 421.05 420.18 113. CH₃ Br 0 CH₂-[3-CH₃-1,1-(Cl)₂- 3.076 360.05 359.31 cyclopropan-2-yl] 114. CH₃ Br 0 CH₂-tetrahydrothio- 3.673 399.95 398.17 pyran-3-yl 115. CH₃ Br 0 CH₂[2,5-(Cl)₂Ph] 3.839 420.95 420.18 116. CH₃ Br 0 CH₂(2-FPh) 3.476 370 369.28 117. CH₃ Br 0 CH₂(4-FPh) 3.464 370.05 369.28 118. CH₃ Br 0 CH₂[4-(NO₂)Ph] 3.215 397 396.29 119. CH₃ Br 0 CH₃ 2.863 276 275.19 120. H CH₃ 0 CH₂Ph 3.000 273.05 272.39 121. H CH₃ 0 CH₂-i-C₃H₇ 2.904 239.05 238.38 122. H CH₃ 0 2-(C₂H₅O)Ph 2.965 303.1 302.42 123. H CH₃ 0 2-(CH₃O—CH₂CH₂O)C₂H₄ 1.877 285.05 284.4 124. H CH₃ 0 CH═CH₂ 2.427 223.05 222.33 125. H CH₃ 0 n-C₄H₉ 2.934 239.15 238.38 126. H CH₃ 0 CH₂[3-(CF₃)Ph] 3.095 341.05 340.39 127. H CH₃ 0 CH₂CF₃ 2.584 265.05 264.29 128. H CH₃ 0 CH₂(3-ClPh) 3.103 307.05 306.84 129. H CH₃ 0 CH₂CH₂(4-NO₂Ph] 2.794 332.05 331.42 130. H CH₃ 0 CH₂[3-(OCF₃)Ph] 3.157 357.05 356.39 131. H CH₃ 0 CH₂[4-(OCF₃)Ph] 3.151 317.15 316.45 132. H CH₃ 0 CH₂C(CH₃)═CH₂ 2.711 237.1 236.36 133. H CH₃ 0 [2-CH₃-5-(NO₂)furyl] 2.373 308.05 307.35 134. H CH₃ 0 CH₂[3,5-(OCH₃)₂Ph] 2.719 333.1 332.45 135. H CH₃ 0 c-C₅H₉ 2.992 251.15 250.39 136. H CH₃ 0 4-CH₃-c-C₆H₁₀ 3.365 279.15 278 137. H CH₃ 0 CH═C(CH₃)₂ 2.736 237.05 236.36 138. H CH₃ 0 CH₂-tetrahydropy- 2.936 297.05 296.48 ran-3-yl 139. H CH₃ 0 CH₂CH₂CH═CH₂ 2.759 237.05 236.36 140. H CH₃ 0 n-C₃H₇ 2.66 225.05 224.35 141. H CH₃ 0 CH₂-t-C₄H₉ 3.196 253.15 252.4 142. H CH₃ 0 C(CH₃)═CH₂ 2.443 223.05 222.33 143. H CH₃ 0 c-C₄H₇ 2.726 237.1 236.36 144. H CH₃ 0 CH₂[2,6(F)₂Ph] 2.905 309.05 308.37 145. H CH₃ 0 CH₂CHF₂ 2.321 247.05 246.3 146. H CH₃ 0 CH₂-c-C₃H₅ 2.707 237.1 236.36 147. H CH₃ 0 CH₂[2-(Ph)Ph] 3.347 349.15 348.49 148. H CH₃ 0 CH₂[3,4-(Cl)₂Ph] 3.276 342.05 341.28 149. H CH₃ 0 CH₂-[3-CH₃-1,1-(Cl)₂- 2.36 281.15 280.41 cyclopropan-2-yl] 150. H CH₃ 0 CH₂-tetrahydrothio- 3.205 320.05 319.28 pyran-3-yl 151. H CH₃ 0 CH₂[2,5-(Cl)₂Ph] 3.363 342.05 341.28 152. H CH₃ 0 CH₂[2-(CF₃)Ph] 3.21 341.05 340.39 153. H CH₃ 0 CH₂(2-FPh) 2.956 291.05 290.38 154. H CH₃ 0 CH₂(4-FPh) 2.926 291.05 290.38 155. H CH₃ 0 CH₂(4-(NO₂)Ph) 2.699 318.1 317.39 156. H CH₃ 0 CH₃ 1.798 197.05 196.29 157. H Cl 1 n-C₄H₉ 158. H Cl 1 (CH₂)₂CH═CH₂ 159. H Cl 1 (CH₂)₂Ph 160. H Cl 1 (CH₂)₂(4-ClPh) 161. H Cl 1 c-C₅H₉ 162. H Cl 1 n-C₃H₇ 163. H Cl 1 CH₂CH═CH₂ 164. H Cl 1 C₂H₅ 165. H Cl 1 CH₂-c-C₃H₇ 166. H Cl 1 (CH₂)₃COOC₂H₅ 167. H Cl 1 CH₂CH₂OPh 168. H Cl 1 CH₂O(4-ClPh) 169. H Cl 1 CH₂Ph 170. H Br 1 C₂H₅ 171. H Br 1 nC₄H₉ 172. H Br 1 CH₂-i-C₃H₇ 173. H Br 1 CH₂CH₂-t-Bu 174. H Br 1 CH₂CH₂-i-Pr 175. H Br 1 i-C₃H₇ 176. H Br 1 CH₂-c-C₃H₉ 177. H Br 1 CH₂-c-C₄H₇ 178. H Br 1 CH₂-c-C₆H₁₁ 179. H Br 1 CH₂(4-(CF₃)Ph) 180. H Br 1 CH₂Ph 181. H Br 1 CH₂C═CH₂(CH₃) 182. H Br 1 CH₂CH═(CH₃)₂ 183. H Br 1 CH₂Si(CH₃)₃ 184. H Br 1 CH₂OC₈H₁₇ 185. H Br 1 CH₂CH₂CN 186. H Br 1 (CH₂)₃COOC₂H₅ 187. H Br 1 CH₂CH₂OPh 188. H Br 1 (CH₂)₃-4-Pyridyl 189. H Br 1 n-C₄H₉ 190. H Br 1 CH₂CH₂-t-Bu 191. H Br 1 CH₂CH₂-i-C₃H₇ 192. H Br 1 CH₂-c-C₃H₅ 193. H Br 1 CH₂-c-C₆H₁₁ 194. H Br 1 CH₂Ph 195. H Br 1 CH₂CH₂OPh 196. H H 1 CH₂Ph 2.24 275 274.37 197. H H 1 CH₂-i-C₃H₇ 2.105 241.05 240.35 198. H H 1 2-(C₂H₅O)Ph ?? 2.289 305.05 304.39 199. H H 1 2-(CH₃O—CH₂CH₂O)C₂H₄ 1.477 287.15 286.37 200. H H 1 n-C₄H₉ 2.134 241.05 240.35 201. H H 1 CH₂[3-(CF₃)Ph] 2.522 343 342.36 202. H H 1 CH₂CF₃ 1.89 268 266.27 203. H H 1 CH₂(3-ClPh) 2.522 309.85 308.81 204. H H 1 CH₂CH₂[4-(NO₂)Ph] 2.174 334 333.39 205. H H 1 CH₂[3-(OCF₃)Ph] 2.596 359 358.36 206. H H 1 CH₂[4-(OCF₃)Ph] 2.526 319 318.42 207. H H 1 CH₂[3,5-(OCH₃)₂Ph] 2.102 335.05 334.42 208. H CH₃ 1 c-C₅H₉ 3.556 330.05 329.28 209. H CH₃ 1 4-CH₃-c-C₆H₁₀ 3.894 358.1 357 210. H CH₃ 1 CH═C(CH₃)₂ 3.186 315.05 315.26 211. H CH₃ 1 CH₂CH₂CH═CH₂ 3.394 316.05 315.26 212. H CH₃ 1 n-C₃H₇ 3.359 304.05 303.24 213. H CH₃ 1 CH₂-t-C₄H₉ 3.661 332.05 331.3 214. H CH₃ 1 C(CH₃)═CH₂ 3.208 302.95 301.23 215. H CH₃ 1 c-C₄H₇ 3.376 316.05 315.26 216. H CH₃ 1 CH₂[2,6-(F)₂-Ph] 3.463 388.95 387.27 217. H CH₃ 1 CH₂CHF₂ 3.011 326.95 325.2 218. H CH₃ 1 CH₂-c-C₃H₅ 3.338 316.05 315.26 219. H CH₃ 1 CH₂[2-(Ph)Ph] 3.812 428.05 427.39 220. H CH₃ 1 CH₂[3,4-(Cl)₂Ph] 3.73 421.95 420.18 221. H CH₃ 1 CH₂[2,5-(Cl)₂Ph] 3.839 422.05 420.18 222. H CH₃ 1 CH₂(2-FPh) 3.527 370 369.28 223. H CH₃ 1 CH₂(4-FPh) 3.464 370.05 369.28 224. H CH₃ 1 CH₂[4-(NO₂)Ph] 3.215 397 396.29 225. H CH₃ 1 CH₃ 2.863 277 275 226. H Cl 2 CH₃ 227. H Cl 2 (CH₂)₂CH═CH₂ 228. H Cl 2 n-C₄H₉ 229. H Cl 2 (CH₂)₂(4-ClPh) 230. H Cl 2 (CH₂)₂Ph 231. H Cl 2 i-C₃H₇ 232. H Cl 2 c-C₅H₁0 233. H Cl 2 n-C₃H₇ 234. H Cl 2 C₂H₅ 235. H Cl 2 CH₂CH═CH₂ 236. H Cl 2 CH₂CH₂OPh 237. H Cl 2 CH₂[4-(CF₃)Ph] 238. H Cl 2 CH₂Ph 239. H Br 2 C₂H₅ 240. H Br 2 n-C₃H₇ 241. H Br 2 n-C₄H₉ 242. H Br 2 CH₂-i-C₃H₇ 243. H Br 2 CH₂CH₂-t-C₄H₉ 244. H Br 2 CH₂CH₂-i-C₃H₇ 245. H Br 2 i-C₃H₇ 246. H Br 2 CH₂-c-C₃H₅ 247. H Br 2 CH₂-c-C₄H₇ 248. H Br 2 CH₂-c-C₆H₁₁ 249. H Br 2 CH₂[4-(CF₃)Ph] 250. H Br 2 CH₂Ph 251. H Br 2 c-C₅H₉ 252. H Br 2 c-C₆H₁₁ 253. H Br 2 c-C₇H₁₃ 254. H Br 2 c-C₈H₁₅ 255. H Br 2 CH₂CH═CH₂ 256. H Br 2 CH₂C═CH(CH₃) 257. H Br 2 CH₂SCH₃ 258. H Br 2 (CH₂)₃COOC₂H₅ 259. H Br 2 CH₂CH₂OPh 260. H Br 2 CH₃ 261. H CF₃ 2 CH₂CH₂OSi(CH₃)₂t-C₄H₉ 262. H Br 2 CH₂Si(CH₃)₂t-C₄H₉ 263. H Br 2 CH₂-c-C₄H₇ 264. H CH₃ 2 n-C₃H₇ 265. H CH₃ 2 CH₂-i-C₃H₇ 266. H CH₃ 2 CH(CH₃)-n-C₃H₇ 267. H CH₃ 2 CH(CH₃)-n-C₆H₁₃ 268. H CH₃ 2 c-C₆H₁₁ 269. H CH₃ 2 c-C₇H₁₃ 270. H CH₃ 2 c-C₈H₁₅ 271. H CH₃ 2 CH(CH₃)CONH₂ 272. H CH₃ 2 CH₂SO₂Ph 273. H CH₃ 2 C₂H₅ 274. H CH₃ 2 CH₂CH₂-i-C₃H₇ 275. H CH₃ 2 CH₂-c-C₃H₇ 276. H CH₃ 2 CH₂Ph 277. H CH₃ 2 CH₂CH₂OPh 278. H CH₃ 2 (CH₂)₃-4-Pyridyl 279. H H 2 CH₂Ph 2.225 291 290.36 280. H H 2 CH₂-i-C₃H₇ 2.242 257.05 256.35 281. H H 2 2-(C₂H₅O)Ph 2.388 321.05 320.39 282. H H 2 2-(CH₃O—CH₂CH₂O)C₂H₄ 1.571 303.05 302.37 283. H H 2 n-C₄H₉ 2.253 257.05 256.35 284. H H 2 CH₂[3-(CF₃)Ph] 2.629 359.05 358.36 285. H H 2 CH₂CF₃ 2.109 283 282.26 286. H H 2 CH₂[3-ClPh] 2.522 325.95 324.81 287. H H 2 CH₂CH₂[4-(NO₂)Ph] 2.235 350.05 349.39 288. H H 2 CH₂[3-(OCF₃)Ph] 2.708 375.05 374.36 289. H H 2 CH₂[4-(OCF₃)Ph] 2.532 335.05 334.42 290. H H 2 CH₂[3,5-(OCH₃)₂Ph] 2.213 351.05 350.42 291. CH₃ Br 2 CH₂Ph 2.729 384.9 383.29 292. CH₃ Br 2 CH₂-i-C₃H₇ 2.771 350.9 349.47 293. CH₃ Br 2 2-(C₂H₅O)Ph 2.797 414.9 413.31 294. CH₃ Br 2 2-(CH₃O—CH₂CH₂O)C₂H₄ 2.293 395.9 395.3 295. CH₃ Br 2 nC₄H₉ 2.772 350.9 349.27 296. CH₃ Br 2 CH₂[3-(CF₃)Ph] 3.001 452.9 451.29 297. CH₃ Br 2 CH₂[3-(Cl)Ph] 2.951 418.8 417.73 298. CH₃ Br 2 CH₂CH₂[4-(NO₂)Ph] 2.653 442.9 442.13 299. CH₃ Br 2 CH₂[4-(OCF₃)Ph] 3.063 468.9 467.29 300. CH₃ Br 2 CH₂[3,5-(OCH₃)₂Ph] 2.770 444.9 443.34 301. CH₃ Br 2 CH₂CF₃ 2.638 375.9 375.19 302. H CH₃ 2 CH₂Ph 2.545 305 304.39 303. H CH₃ 2 CH₂-i-C₃H₇ 2.320 271 270.37 304. H CH₃ 2 2-(C₂H₅O)Ph 2.382 335 334.42 305. H CH₃ 2 2-(CH₃O—CH₂CH₂O)C₂H₄ 1.711 317 316.4 306. H CH₃ 2 n-C₄H₉ 2.308 271 270.37 307. H CH₃ 2 CH₂[3-(CF₃)Ph] 2.798 373 372.39 308. H CH₃ 2 CH₂CF₃ 2.166 296.9 296.29 309. H CH₃ 2 CH₂[3-(Cl)Ph] 2.581 339.5 338.84 310. H CH₃ 2 CH₂CH₂[4-(NO₂)Ph] 2.293 364 363.42 311. H CH₃ 2 CH₂[4-(OCF₃)Ph] 2.574 349.9 348.39

[0080] n-C_(m)H_(2m-1): n-alkyl;

[0081] c-C_(m)H_(2m-1): cycloalkyl;

[0082] i-C₃H₇: isopropyl;

[0083] t-C₄H₉: tert. butyl;

[0084] Ph: C₆H₅

[0085] 2-FPh: 2-fluorophenyl;

[0086] 4-FPh: 4 fluorophenyl;

[0087] 3-ClPh: 3 chlorophenyl;

[0088] 4-ClPh: 4 chlorophenyl;

[0089] 2-(CF₃)Ph: 2-(trifluoromethyl)phenyl;

[0090] 3-(CF₃)Ph: 3-(trifluoromethyl)phenyl;

[0091] 4-(CF₃)Ph: 4-(trifluoromethyl)phenyl;

[0092] 3-(OCF₃)Ph: 3-(trifluoromethoxy)phenyl;

[0093] 4-(OCF₃)Ph: 4-(trifluoromethoxy)phenyl;

[0094] 4-(NO₂)Ph: 4-nitrophenyl;

[0095] 2-(C₂H₅O)Ph: 2-ethoxyphenyl;

[0096] CH₂(4-FPh):

[0097] CH₂(2-FPh):

[0098] 2-(Ph)Ph: o-biphenyl

[0099] 3,5-(OCH₃)₂Ph: 3,5-bis(methoxy)phenyl;

[0100] 2,6-(F)₂Ph: 2,6-difluorophenyl;

[0101] 3,4-(Cl)₂Ph: 3,4-dichlorophenyl;

[0102] 2,5-(Cl)₂Ph: 2,5-dichlorophenyl;

[0103] 2-CH₃-5-(NO₂)furyl: 2-methyl-5-nitrofuryl;

[0104] The compounds of the formula I can be obtained according to the following reaction sequence shown in scheme 1:

[0105] In the formulae I, II, II and IV, the variables A, R, R¹, R², R³ have the meanings as defined above. Hal denotes bromine or iodine. Halide means chloride, bromide or iodide.

[0106] In step a) 2-aminopyridines of the formula II are first halogenated to yield the 3-halo-2-amino pyridines of the formula III. Usually the bromination is carried out with bromine [cf.: A. Fuss, V. Koch, Synthesis 1990, 681-685; M. Tonga, J. Bupp, T. Tochimoto, J. Heterocycl. Chem. 1994, 31, 1641-1644] or N-bromosuccinimide (NBS) [cf. : J. Mouton, M. Schmitt, V. Collort, J. Bourguignon, Heterocycles 1997, 45, 897-910; R. Beugelmans, M. Chban, Bull. Soc. Chim. France, 1995, 132, 290-305]. The iodination can be accomplished by treatment of the 2-aminopyridines of the formula II with iodine or ICl [cf.: M. V. Jovanovic, Heterocycles 1994, 22, 1195-1210]. Particular preference is given to the bromination with bromine.

[0107] Advantageously the halogenation is carried out with at least one molar equivalent of halogen, preferably with 1.05 to 1.5 molar equivalents of halogen. The reaction is usually carried out in an inert organic solvent. Suitable solvents are carboxylic acids, preferably C₂-C₅-carboxylic acids, such as acetic acid, propionic acid, butyric acid and valeric acid, and cyclic or acyclic hydrocarbons, such as n-pentane, n-hexane, n-heptane, n-octane, petroleum ether, cyclohexane, or halogenated solvents, such as dichloromethane, trichloromethane. It is also possible to use mixtures of these solvents.

[0108] The halogenation is usually carried out at a temperature from 0° C. to the boiling point of the solvent, preferably from 10° C. to 70° C.

[0109] The reaction mixtures are worked up in a customary fashion. The compounds III can be accompanied by side products resulting from the formation of regioisomers or double bromination. These side products can be removed by column chromatography or crystallisation.

[0110] Alternatively, as shown in scheme 2, it is possible to prepare the compound III according to the procedures described by L. Estel, F. Marsais, G. Queguiner, J. Org. Chem. 1988, 53, 2740-2744.

[0111] Initially the amino group is protected, for example by acylation. The pivaloyl group is a useful aminoprotecting group and can be introduced into II, e. g. by a method described by L. Estel, F. arsais, G. Queguiner, J. Org. Chem. 1988, 53, 2740-2744. Then the corresponding 3-lithiopyridine is prepared by addition of a lithiumorganic compound, such as n-butyl- or t-butyllithium, phenyllithium or preferably in the presence of a secondary amine such as diisopropylamine, 2,2,6,6-tetramethylpiperidine or dicyclohexylamine or by addition of the corresponding lithium amides, such as lithium diisopropylamide, lithium 2,2,6,6-tetramethylpiperidide, lithium dicyclohexylamide or hexamethyldisilazane. In general more than one molar equivalent of lithiumorganic compound, preferably 1.1 to 5 molar equivalents, based on compound II, are required for the metallation. The resulting organolithium compounds are converted into the compound III by subsequent addition of iodine and cleavage of the protecting group. Usually a slight molar excess of iodine is used. The protecting group is removed for example by reacting III′ with acids or bases, e.g. hydrochloric acid ( Heterocycles, 1994, 39, S. 271) or lithium hydroxide (Tetrahedron Letters, 1997, 38, 4037).

[0112] The metallation and iodination are usually carried out at from −100° C. to 50° C., preferably at from −80° C. to 20° C. in an inert organic solvent. Suitable solvents are ethers, for example diethyl ether, methyl-tert-butylether, diisopropylether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, alkanes, for example n-pentane, n-hexane, n-heptane, n-octane, petroleum ether and cyclohexane or mixture thereof.

[0113] The starting material, i. e. 2-aminopyridines of the formula II, required for preparing the compounds I are known from literature, or can be prepared by known methods [cf.: Pozharskii, Simonov, Doron'kin, Russ. Chem. Rev. 1978, 47, 1042-1060].

[0114] In step b) the compounds of formula III are treated with a potassium salt of a xanthogenic ester, preferably ethylxanthogenic acid potasssium salt, to yield the corresponding 2-thio thiazolo [4,5-b]pyridines of formula IV. The cyclization can be conducted similarly to the preparation of benzothiazoles from o-haloamilines, as described by N. C. Chaudhuri, Synth. Commun. 1996, 26, 3783-3790; N. Suzuki, Y. Tanaka, R. Dohrnari, Chem. Pharm. Bull. 1079, 27, 1-11. Preferably compound III is treated with 1.5 to 5 molar equivalents of the potassium salt. The reaction is usually carried out in an polar solvent, e. g. water and/or alcohols, and/or aprotic polar solvents such as amides, e.g. N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl pyrrolidone or sulfoxides, e-g. dimethyl sulfoxide or mixture thereof. Preferably the reaction is conducted in N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl pyrrolidone or mixtures thereof. The use of aprotic polar solvents and additional water as cosolvent is possible (see EP-A 35219). In this case the amount of water is about 10 to 200% by weight based on the amount of organic solvent. The reaction is usually carried out at a temperature of from 25° C. to 250° C., preferably of from 60° C. to 210° C., especially above 180° C.

[0115] In step c) the group R is introduced to yield the thiazolo [4,5-b]pyridines of formula I, wherein n is 0. In order to obtain compounds I compounds IV can be reacted with an organic halide of the formula R-A-halide in the presence of a base. Halide means chloride, bromide or iodide. Bases which may be used are well known to those skilled in the art and are for example alkali carbonates, such as lithium carbonate, sodium carbonate, potassium carbonate, bicarbonates, such as magnesium carbonate, magnesium carbonate, alkali metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide. Particular preference is given to sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide and potassium ethoxide. In general a slight excess of the organic halide is used, preferably in the range of 1,1 to 2 molar equivalents. The reaction is usually carried out in polar aprotic solvents, e. g. N,N-dimethylformanide, N,N-dimethylacetamide, N-methyl pyrrolidone, ethers such as tetrahydrofuran, diethyl ether, methyl-tert.-butyl ether, sulfoxides, such as dimethyl sulfoxide or mixtures thereof, preferably in tetrahydrofuran, diethyl ether, methyl-tert.-butyl ether, N, N-dimethylformamide, N,N-dimethylacetamide, N-methyl pyrrolidone or dimethylsulfoxide. The reaction is usually carried out at a temperature of about 0° C. to 200° C., preferably at a temperature of about 20° C. to 150° C.

[0116] Alternatively, the compounds I, wherein the radical -A-R represents an olefinically unsaturated group, can be prepared by reacting the compound IV with an aliphatic or cyclic aldehyde having an α-hydrogen in the presence of a Lewis acid, e. g. according to Mukaiama and Saigo, Chem. Lett. 479 (1973) or Akiyania, Bull. Chem. Soc. Jpn. 50, 936 (1977).

[0117] In formula I, n can also be 1 or 2. The sulfide compound I with n=0 can be converted into to the sulfoxide compound I with n=1 by an approximately equimolar amount of hydrogen peroxide or by treatment with other oxidising agents such as tert.-butyl hydroperoxide or peracids, e. g. m-chloro perbenzoic acid, peracetic acid (step d)). The sulfoxide compound can be further oxidised to the sulfone compound I with n=2 by another mole of oxidising agent. The sulfide compound I (n=0) can be directly converted into the sulfone compound I (n=2) without isolation of the sulfoxide (step e)). Suitable solvents for step d) and e) are halogenated alkanes, such as dichloromethane, chloroform, tetrachloromethane or chlorobenzene, alkohols, such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, amides as dimethylformamide, dimethylacetamide, cyclic or acyclic alkanes such as cyclohexane, hexane, pentane, heptane, petroleum ether. Preferred solvents are dichloromethane and chloroform. Usually the oxidation is carried out at about −80° C. to 100° C., preferably at about −20° C. to 50° C.

[0118] The compounds I are suitable as fungicides. They have outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them act systemically, and they can be employed in crop protection as foliar- and soilacting fungicides.

[0119] They are especially important for controlling a large number of fungi on a variety of crop plants such as wheat, rye, barley, oats, rice, maize, grass, bananas, cotton, soya, coffee, sugar cane, grapevines, fruit species, ornamentals and vegetables such as cucumbers, beans, tomatoes, potatoes and cucurbits, and on the seeds of these plants.

[0120] Specifically, they are suitable for controlling the following plant diseases:

[0121] Alternaria species on vegetables and fruit, Botrytis cinerea (gray mold) on strawberries, vegetables, ornamentals and grapevines, Cercospora arachidicola on peanuts, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits, Erysiphe graminis (powdery mildew) on cereals, Fusarium and Verticillium species on various plants, Helminthosporium species on cereals, Mycosphaerella species on bananas and peanuts, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on grapevines, Podosphaera leucotricha on apples, Pseudocercosporella herpotrichoides on wheat and barley, Pseudoperonospora species on hops and cucumbers, Puccinia species on cereals, Pyricularia oryzae on rice, Rhizoctonia species on cotton, rice and lawns, Septoria nodorum on wheat, Uncinula necator on grapevines, Ustilago species on cereals and sugar cane, and Venturia species (scab) on apples and pears.

[0122] Moreover, the compounds I are suitable for controlling harmful fungi such as Paecilomyces variotii in the protection of materials (e.g. wood, paper, paint dispersions, fibers and tissues) and in the protection of stored products.

[0123] The compounds I are applied by treating the fungi, or the plants, seeds, materials or the soil to be protected against fungal infection, with a fungicidally active amount of the active ingredients. Application can be effected both before and after infection of the materials, plants or seeds by the fungi.

[0124] In general, the fungicidal compositions comprise from 0.1 to 95, preferably 0.5 to 90,% by weight of active ingredient.

[0125] When used in crop protection, the rates of application are from 0.01 to 2.0 kg of active ingredient per ha, depending on the nature of the effect desired.

[0126] In the treatment of seed, amounts of active ingredient of from 0.001 to 0.1 kg, preferably 0.01 to 0.05 kg, are generally required per kilogram of seed.

[0127] When used in the protection of materials or stored products, the rate of application of active ingredient depends on the nature of the field of application and on the effect desired. Rates of application conventionally used in the protection of materials are, for example, from 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active ingredient per cubic meter of material treated.

[0128] The compounds I can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular purpose; in any case, it should guarantee a fine and uniform distribution of the compound according to the invention.

[0129] The formulations are prepared in a known manner, e.g. by extending the active ingredient with solvents and/or carriers, if desired using emulsifiers and dispersants, it also being possible to use other organic solvents as auxiliary solvents if water is used as the diluent. Auxiliaries which are suitable are essentially: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. mineral oil fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) and water; carriers such as ground natural minerals (e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g. highly-disperse silica, silicates); emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin -sulfite waste liquors and methylcellulose.

[0130] Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylaryl-sulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids and their alkali metal and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ether, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of napthalenesulfonic acid with phenol or formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methylcellulose.

[0131] Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, e.g. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and water.

[0132] Powders, materials for scattering and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.

[0133] Granules, e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Examples of solid carriers are mineral earths, such as silicas, silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

[0134] In general, the formulations comprise of from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

[0135] The following are exemplary formulations:

[0136] I. 5 parts by weight of a compound according to the invention are mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dust which comprises 5% by weight of the active ingredient.

[0137] II. 30 parts by weight of a compound according to the invention are mixed intimately with a mixture of 92 parts by weight of pulverulent silica gel and 8 parts by weight of paraffin oil which had been sprayed onto the surface of this silica gel. This gives a formulation of the active ingredient with good adhesion properties (comprises 23% by weight of active ingredient).

[0138] III. 10 parts by weight of a compound according to the invention are dissolved in a mixture composed of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid N-monoethanolamide, 2 parts by weight of calcium dodecylbenzenesulfonate and 2 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil (comprises 9% by weight of active ingredient).

[0139] IV. 20 parts by weight of a compound according to the invention are dissolved in a mixture composed of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 5 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil (comprises 16% by weight of active ingredient).

[0140] V. 80 parts by weight of a compound according to the invention are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalene -alpha-sulfonate, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill (comprises 80% by weight of active ingredient).

[0141] VI. 90 parts by weight of a compound according to the invention are mixed with 10 parts by weight of N-methyl-α-pyrrolidone, which gives a solution which is suitable for use in the form of microdrops (comprises 90% by weight of active ingredient).

[0142] VII. 20 parts by weight of a compound according to the invention are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

[0143] VIII. 20 parts by weight of a compound according to the invention are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalene -α-sulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives a spray mixture which comprises 0.1% by weight of the active ingredient.

[0144] The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading, or granules, by means of spraying, atomizing, dusting, scattering or pouring. The use forms depend entirely on the intended purposes; in any case, this is intended to guarantee the finest possible distribution of the active ingredients according to the invention.

[0145] Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.

[0146] The active ingredient concentrations in the ready-to-use products can be varied within substantial ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%.

[0147] The active ingredients may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active ingredient, or even the active ingredient without additives.

[0148] Various types of oils, herbicides, fungicides, other pesticides, or bactericides may be added to the active ingredients, if appropriate also only immediately prior to use (tank mix). These agents can be admixed with the agents according to the invention in a weight ratio of 1:10 to 10:1.

[0149] In the use form as fungicides, the compositions according to the invention can also be present together with other active ingredients, e.g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers. Mixing the compounds I or the compositions comprising them in the use form as fungicides with other fungicides frequently results in a broader fungicidal spectrum of action.

[0150] The following list of fungicides, together with which the compounds according to the invention can be used, is intended to illustrate the possible combinations, but not to impose any limita- tion:

[0151] sulfur, dithiocarbamates and their derivatives, such as iron(III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebis-dithiocarbamate, manganese zinc ethylenediaminebisdithiocarbamate, tetramethylthiuram disulfide, ammonia complex of zinc (N,N-ethylenebisdithiocarbamate), ammonia complex of zinc (N,N′-propylenebisdithiocarbamate), zinc (N,N′-propylenebisdithiocarbanate), N,N′-polypropylenebis(thiocarbamoyl)disulfide;

[0152] nitro derivatives, such as dinitro(1-methylheptyl)phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl 5-nitro-isophthalate;

[0153] heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, O, O-diethyl phthalimidophosphonothioate, 5-amino-1-[bis(dimethylamino)phosphinyl]-3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithiolo[4,5-b]quinoxaline, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate, 2-methoxycarbonylaminobenzimidazole, 2-(2-furyl)benzimidazole, 2-(4-thiazolyl)benzimidazole, N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfodiamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, pyridine-2-thiol 1-oxide, 8-hydroxyguinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine 4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran -3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide, 2,4,5-trimethylfuran-3-carboxanilide, N-cyclohexyl- 2,5-dimethylfuran -3-carboxamide, N-cyclohexyl-N-methoxy-2,5-dimethylfuran -3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholine-2,2,2-trichloroethyl acetal, piperazine -1,4-diylbis-1-(2,2,2-trichloroethyl)formamide, 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane;

[0154] 2,6-dimethyl-N-tridecylmorpholine or its salts, 2,6-dimethyl-N-cyclododecylmorpholine or its salts, N-[3-(p-tert-butylphenyl) -2-methylpropyl]-cis-2,6-dimethyl- morpholine, N[3-(p-tert-butylphenyl)-2-methylpropyl]-piperidine, 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole, 1-[2-(2,4-dichlorophenyl)-4-n-propyl -1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole, N-(n-propyl) -N-(2,4,6-trichlorophenoxyethyl)-N′-imidazolylurea, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-l-yl)-2-butanone, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol, (2RS,3RS)-1-(3-(2-chlorophenyl)-2-(4-fluorophenyl)-oxiran-2-ylmethyl]-1H-1,2,4-triazole, α-(2-chlorophenyl)-α-(4-chlorophenyl) -5-pyrimidinemethanol, 5-butyl-2-dimethylamino-4-hydroxy -6-methylpyrimidine, bis(p-chlorophenyl)-3-pyridinemethanol, 1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene, 1,2-bis(3-methoxycarbonyl-2-thioureido)benzene, strobilurines such as methyl E-methoxyimino- [α-(o-tolyloxy) -o-toly]acetate, methyl E-2-{2-[6-(2-cyanophenoxy)pyrimidin -4-yloxy]-phenyl}-3- methoxyacrylate, methyl-E-methoxyimino -[α-(2-phenoxyphenyl)]-acetamide, methyl E-methoxyimino-[α-(2,5-dimethylphenoxy)-o-tolyl]acetamide, anilinopyrimidines such as N-(4,6-dimethylpyrimidin-2-yl)aniline, N-[4-methyl-6-(i-propynyl)pyrimidin-2-yl]-aniline, N-[4-methyl-6-cyclopropylpyrimidin-2-yl]aniline, phenylpyrroles such as 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile, cinnamamides such as 3-(4-chlorophenyl)-3-(3,4-dimethoxy-phenyl)acryloylmorpholine, and a variety of fungicides such as dodecylguanidine acetate, 3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide, hexachlorobenzene, methyl N-(2,6-dimethylphe- nyl)-N-(2-furoyl)-DL-alaninate, DL-N-(2,6-dimethylphenyl)-N-(2′-methoxyacetyl)-alanine methyl ester, N-(2,6-dime-thylphenyl)-N-chloroacetyl-D,L-2-aimino- butyrolactone, DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)alanine methyl ester, 5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine, 3-[3,5-dichlorophenyl(5-methyl-5-methoxymethyl]-1,3-oxazolidine-2,4-dione, 3-(3,5-dichlorophenyl) -1-isopropylcarbamoylhydantoin, N-(3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano-[N-(ethylaminocarbonyl)-2-methoximinolacetamide, 1-(2-(2,4-dichloro-phenyl)pentyl]-1H-1,2,4-triazole, 2,4-difluoro-α-(1H-1,2,4-triazolyl-1-methyl)benzhydryl alcohol, NN-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5trifluoromethyl-3-chloro-2-aminopyridine, 1-((bis(4-fluorophenyl)methylsilyl)methyl) -1H-1,2,4-triazole.

SYNTHESIS EXAMPLES Example 1 6-Chloro-2-[(3-allyl)thio]thiazolo(4,5-b]pyridine

[0155]

[0156] 1.1 2-Amino-3-bromo-5-chloropyridine

[0157] A solution of 257 g (1.61 mol) of bromine in 380 ml of acetic acid was added dropwise over a period of one hour to a solution of 187 g (1.45 mol) of 2-amino-5-chloropyridine in 1.5 of acetic acid. The reaction mixture was refluxed for 3 h and then allowed to cool to ambient temperature. 1-9 l of demineralized water were added and the mixture was concentrated in vacuo. The residue was partitioned between 4 l of ethyl acetate and 1.8 l of water. The mixture was basified with 3 l of a 10% by weight aqueous sodium hydroxide solution. The organic layer was separated and washed with brine (2×1.5 l), dried over magnesium sulfate, filtered and concentrated in vacuo. The residue was filtered, washed with hexane (2×100 ml) and dried in vacuo to give 192 g of 2-amino-3-bromo-5-chloropyridine. The mother liquor was concentrated in vacuo, filtered, washed with hexane and dried to give further 75 g of the same product.

[0158] 1.2 6-Chloro-2-mercaptothiazolo[4,5-b]pyridine

[0159] A solution of 133 g (0.64 mol) of 2-amino-3-bromo-5-chloropyridine from Example 1.1 in 1.02 1 of N-methylpyrrolidone was admixed with 205 g (1.28 mol) O-ethylxanthic acid potassium salt. The reaction mixture was refluxed for 6 h and then allowed to cool to ambient temperature. 2.7 l of demineralized water were added then acetic acid to adjust the reaction mixture to pH 4.5. The resulting precipitate was filtered, washed with demineralized water (2×600 ml). The solid was triturated in succession with demineralized water (2×4.2 l) and ethanol, (1.5 l), filtered, washed with ethanol (2×300 ml) followed by hexane (2×400 ml) and dried in vacuo at 45° C. to give 127 g (yield: 98%) of 6-chloro-2-mercaptothiazolo[4,5-b]pyridine used without further purification.

[0160] 1.3 6-Chloro-2-[(3-allyl)thio]thiazolo[4,5-b]pyridine

[0161] To a stirred solution of 0.3 g (17 mmol) of the thiol from Example 1.2 in 1 ml of dimethylformamide was added a solution of 0.3 g (2.52 mmol) of allylbromide in 1 ml of dimethylformamide and 0.3 g (1.8 mmol) of potassium carbonate. The reaction mixture was stirred at 90° C. for 12 h and then allowed to cool to ambient temperature. 2 ml of demineralized water were added and the mixture was then extracted with dichloromethane. The organic layer was washed with water (2×5 ml), dried over sodium sulfate, filtered and then concentrated in vacuo to yield 0.4 g of the title product.

Example 2 6-Chloro-2-[(3-allylsulfinyl]thiazolo[4,5-b]pyridine

[0162]

[0163] To a solution of 0.03 g (0.1 mmol) of 6-chloro-2-[(3-allyl)thio]thiazolo[4,5-b]pyridine from Example 1.3 in 2 ml of a 2:1 mixture of dichloromethane and acetic acid were added 13 ml (0.4 mmol) of a 30% by weight aqueous solution of hydrogen peroxide. The solution was stirred for 12 h at ambient temperature. The reaction solution was diluted with 3 ml of water and then extracted with 4 ml of dichloromethane. The organic layer was washed with 3 ml of an aqueous solution of Na₂S₂O₄, dried over sodium sulfate and then concentrated in vacuo to give 0.04 g of the title compound.

Example 3 6-Chloro-2-(methylthio)thiazolo[4,5-b]pyridine

[0164]

[0165] 328 g (2.31 mol) of methyl iodide were added dropwise to a stirred suspension of 363 g (2.62 mol) of potassium carbonate and 354 g (1.75 mol) of 6-chloro-2-mercaptothiazolo[4,5-b]pyridine from Example 1.2 in 2.28 l of dimethylformamide at 5° C. The reaction mixture was stirred at ambient temperature for 68 h and then poured into 4.5 l of demineralized water. The precipitate was filtered, rinsed with water (2×500 ml) and then dried in vacuo at 45° C. to give 308.9 g (yield: 81%) of 6-chloro-2-(methylthio)thiazolo[4,5-b]pyridine.

Example 4 6-Chloro-2-(methylsulfonyl)thiazolo[4,5-b]pyridine

[0166]

[0167] To a solution of 333 g (1.45 mol) 3-chloroperoxybenzoic acid (75% assay) in 2 l of dichloromethane was added a slurry of 120 g (0.55 mol) 6-chloro-2-(methylthio)thiazolo[4,5-b]pyridine from Example 3.1 in 700 ml of dichloromethane in portions over a period of 20 min. The solution was refluxed for 6 h before addition of an additional portion of a solution of 50 g of 3-chloroperoxybenzoic acid in 500 ml dichloromethane. Then the reaction mixture was refluxed for further 2 h. The reaction mixture was allowed to cool to ambient temperature, diluted with dichloromethane (1 1) and then washed with 6 l of a 5% by weight aqueous sodium carbonate solution. The aqueous sodium carbonate layer was extracted with 2 l of dichloromethane. The combined organic layers were washed with 3 l of a saturated aqueous sodium bicarbonate solution followed by 3 l of brine, dried over sodium sulfate, filtered and then concentrated in vacuo to a thick slurry. The residue was taken up in 100 ml of hexane, filtered, washed with 150 ml of a solution of ethyl acetate (20% by volume) in hexane followed by 300 ml of hexane and then dried in vacuo at 45° C. to give 117 g (yield: 85%) of the title compound (m.p. 201-202° C.).

[0168] The compounds I-71 to I-156, I-196 to I-255 and I-279 to I-311, listed in Table 1 were prepared in analogues manner. 

1. A method for controlling harmful fungi, which comprises treating the fungi or the materials, plants, the soil or the seed to be protected against fungal attack with an effective amount of a thiazolo[4,5-b]pyridine of the formula I:

in which the radicals R¹, R², R³, A and the index n have the following meanings: R¹, R², R³: independently of one another are: hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl or phenyl which may be unsubstituted or carry 1, 2, 3 or 4 substituents which are selected, independently of one another, from halogen, nitro, cyano, alkyl, alkoxy, OCHF₂ or CF₃; n: 0,1 or 2; R: hydrogen, cyano, halogen, C₁-C₆-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl, C₂-C₄-alkinyl, C₂-C₄-haloalkinyl, cyano-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₃-C₈-cycloalkyl, tris(C₁-C₄-alkyl)silyl, tris(C₁-C₄-alkyl)silyloxy, COR⁴, COOR⁵, CONR⁶R⁷, S(O)_(k)R⁸, phenyl, phenoxy, a 5 or 6 membered heterocycle, which has 1, 2, or 3 heteroatoms being selected from O, S and N, and which may be saturated, unsaturated or aromatic, wherein phenyl, phenoxy and the heterocycle, independently of each other, may carry 1, 2, 3 or 4 substituents which are selected, independently of one another, from halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, methylsulfonyl, OCHF₂, CF₃ or phenyl, which may carry 1, 2 or 3 radicals selected from halogen, C₁-C₄-alkyl, methylsulfonyl, OCHF₂ or CF₃; wherein k is 0, 1 or 2; R⁴ is hydrogen, C₁-C₆-alkyl, phenyl and phenyl-C₁-C₄-alkyl, wherein phenyl and phenyl-C₁-C₄-alkyl may carry 1, 2, 3 or 4 substituents on the phenyl ring which are selected, independently of one another, from halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, OCHF₂ or CF₃; R⁵ is C₁-C₆-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, phenyl and phenyl-C₁-C₄-alkyl, wherein phenyl and phenyl -C₁-C₄-alkyl may carry 1, 2, 3 or 4 substituents on the phenyl ring which are selected, independently of one another, from halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, OCHF₂ or CF₃; R⁶, R7 independently from one another are hydrogen, C₁-C₆-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, phenyl, and phenyl-C₁-C₄-alkyl, wherein phenyl and phenyl -C₁-C₄-alkyl may carry 1, 2, 3 or 4 substituents on the phenyl ring, which are selected, independently of one another, from halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, OCHF₂ or CF₃; or may together form a 5- or 6-membered heterocycle, which may additionally to the nitrogen atom may have 1 or 2 further heteroatoms selected from N, O or S, R⁸ is C₁-C₆-alkyl, C₁-C₄-haloalkyl, phenyl, and phenyl -C₁-C₄-alkyl, wherein phenyl and phenyl-C₁-C₄-alkyl may carry 1, 2, 3 or 4 substituents on the phenyl ring which are selected, independently of one another, from halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, OCHF₂ or CF₃; A: C₁-C₄-alkylene; or A-R: may together be dihalomethyl, trihalomethyl, C₃-C₈-cycloalkyl, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl, C₅-C₈-cycloalkenyl or a 5 or 6 membered heterocycle, which has 1, 2, or 3 heteroatoms being selected from O, S and N. which may be saturated, unsaturated or aromatic, and which may carry 1, 2, 3 or 4 substituents which are selected, independently of one another, from halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, methylsulfonyl, OCHF₂, CF₃ or phenyl, which may carry 1, 2 or 3 radicals selected from halogen, C₁-C₄-alkyl, methylsulfonyl, OCHF₂ or CF₃, wherein cycloalkyl and cycloalkenyl, may independently carry 1, 2, 3 or 4 substituents, which are selected, independently of one another, from halogen and C₁-C₄-alkyl, and/or may contain a carbonyl or thiocarbonyl ring member; and/or with an agricultural acceptable salt thereof.
 2. A method as claimed in claim 1, where the radical R² in formula I is different from hydrogen.
 3. A method as claimed in claim 1, where the radicals R¹ to R³ in formula I are as defined below; R¹ hydrogen or C₁-C₄-alkyl; R² hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl; R³ hydrogen;
 4. A method as claimed in claim 1, where A in formula I is methylene, 1,2-ethylene, 1,1-ethylene or 1,3-propylene and R is phenyl, phenoxy, a 5 or a 6 membered heterocycle, which has 1, 2, or 3 heteroatoms being selected from O, S and N, wherein phenyl, phenoxy and the heterocycle, independently of each other, may be unsubstituted or substituted as defined above.
 5. A method as claimed in claim 1, where A in formula I is methylene, 1,2-ethylene, 1,1-ethylene or 1,3-propylene and R is selected from cyano, C₁-C₄-alkoxy, cyano-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, tris(C₁-C₄-alkyl)silyl, tris(C₁-C₄-alkyl)silyloxy, COR⁴, COOR⁵, CONR⁶R⁷ or S(O)_(k)R⁸, wherein the radicals R⁴ to R⁸ and the integer k are defined as above.
 6. Thiazolo[4,5-b]pyridines of the formula I

in which the radicals R¹, R², R³, A and the index n are as defined in claim 1 and the agriculturally acceptable salts thereof, except: 2-methylsulfonyl-thiazolo[4,5-b]pyridine, 2-methylsulfonyl-6-bromo-thiazolo[4,5-b]pyridine, 2-methylthio-6-bromo-thiazolo[4,5-b]pyridine, 2-[(methoxycarbonyl)methylsulfinyl]thiazolo[4,5-b]pyridine, 2-[(methoxycarbonyl)methylsulfinyl)-6-trifluoro-thiazolo[4,5-b]pyridine, 2-[(methoxycarbonyl)methylthio]-6-trifluoro-thiazolo[4,5-b]pyridine, and 2-[(methoxycarbonyl)methylthio]thiazolo[4,5-b]pyridine, 2-[(ethoxycarbonyl)methylthio]thiazolo[4,5-b]pyridine, 2-[(4,4,3-trifluoro-3-butenyl)thio]thiazolo[4,5-b]pyridine 2-[(2-propen-1-yl)thio]thiazolo[4,5-b]pyridine, 2-[(cycloproplymethyl)thio]thiazolo[4,5-b]pyridine, 2-[1-(ethoxycarbonyl)ethylthio]thiazolo[4,5-b]pyridine, 2-[(bromodifluoromethyl)thio]thiazolo[4,5-b]pyridine, 2-[(difluoromethyl)thio]thiazolo[4,5-b]pyridine, and 2-[(2,2,2-trifluoroethyl]thiolthiazolo[4,5-b]pyridine.
 7. Thiazolo[4,5-b]pyridines as claimed in claim 6, where the radical R² in formula I is different from hydrogen.
 8. Thiazolo[4,5-b]pyridines as claimed in claim 6, where the radicals R¹ to R³ in formula I are as defined below: R¹ hydrogen or C₁-C₄-alkyl; R² hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl; R³ hydrogen.
 9. Thiazolo[4,5-b]pyridines as claimed in claim 6, where n in formula I is 1 or
 2. 10. Thiazolo[4,5-b]pyridines as claimed in claim 6, where A in formula I is methylene, 1,2-ethylene, 1,1-ethylene or 1,3-propylene and R is phenyl, phenoxy, a 5 or a 6 membered heterocycle, which has 1, 2, or 3 heteroatoms being selected from O, S and N, wherein phenyl, phenoxy and the heterocycle, independently of each other, may be unsubstituted or substituted as defined above.
 11. Thiazolo[4,5-b]pyridines as claimed in claim 6, where A in formula I is methylene, 1,2-ethylene, 1,1-ethylene or 1,3-propylene and R is selected from cyano, C₁-C₄-alkoxy, cyano -C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, tris(C₁-C₄-alkyl)silyl, tris(C₁-C₄-alkyl)silyloxy, COR⁴, COOR⁵, CONR⁶R⁷ or S(O)_(k)R⁸, wherein the radicals R⁴ to R⁸ and the integer k are defined as above.
 12. An agricultural formulation in the form of a directly sprayable solution, powder, suspension, dispersion, emulsion, emulsion concentrate, oil dispersion, paste, dust, a material for spreading, or in the form of granules, comprising at least one thiazolo[4,5-b]pyridine of the formula I defined in claim 1 and/or at least one agriculturally acceptable salt thereof and at least one agriculturally acceptable carrier, which may be liquid or solid. 